Silver halide photographic emulsion



United States Patent ,481,742 SILVER HALIDE PHOTOGRAPHIC EMULSIONYahachi Terashima, Yukio Yasuda, and Tadao Sakai, Kanagawa-ken, Japan,assignors to Fuji Shashin Film Kabushiki Kaisha, Kanagawa-ken, Japan, acorporation of Japan No Drawing. Filed'July 2, 1965, Ser. No. 469,304Claims priority, application Japan, July 11, 1964, 39/319,675 Int. Cl.G03c 1/28, 1/12 US. Cl. 96-104 7 Claims ABSTRACT OF THE DISCLOSURE Asilver halide photographic emulsion Containing a methine dye and acompound shown -by the general formula R-i'I-Ri onto o- I wherein Rrepresents an alkyl group having 8 to 18 carbon atoms; R represents amember selected from the class consisting of CH COOH and (CH CH O) H; Rrepresents a member selected from the class consisting of CH COOH and(CH CH O),,H; and p and q each represents 0 or a positive integer, p+qbeing however 1 to 18.

' The present invention relates to a silver halide photographic emulsionoptically sensitized with a polymethine dye'. U silver halidephotographic emulsion has generally an intrinsic sensitivity to a bluewave length range in avisible spectrum but by incorporating apolymethine dye in the photographic emulsion, the emulsion can beendowed with a photosensitivity to a green wave length range as well astoa red wave length range, which is generally known as sensitization. Inparticular, a high color sensitivity is required in a so-calledpanchromatic black and white photographic film, sensitized to visualwave length region or in a multi-layered color photographic materialconsisting of silver halide emulsion layers each having blue', green andred sensitivity in visual wave length region. A polymethine dye which isadsorbed on a silver halide emulsion and gives a color sensitivity toits silver halide emulsion is known as optical sensitizer and apolymethine dye is generally considered to be different from a chemicalsensitizer which increases the intrinsic sensitivity of a silver halideemulsion.

However, an optical sensitizer cannot always give satisfactory colorsensitivity to silver halide emulsions. The color sensitivity of asilver halide emulsion may be increased incidentally by increasing theintrinsic sensitivity of the silver halide emulsion but the colorsensitivity of the emulsion can be also increased by increasing thecolor sensitizing efiiciency of a polymethine dye for the silver halideemulsion having the same intrinsic sensitivity. In color photographicmaterials, in particular, it is preferable to increase the colorsensitivity by increasing the color sensitizing efficiency to silverhalide photographic emulsions having same intrinsic sensitivity. It iswell known that a super sensitizer is used together with an opticalsensitizer to increase the color sensitizing efficiency (of, C. E. K.Mees, The Theory of the Photographic Process; pages 474-477 (1954),MacMillan Co.). However, a high color sensitizing efliciency is notalways obtained by the use of conventional super sensitizer togetherwith various polymethine dyes. Most conventional super sensitizers areusually effective only when they are used together with polymethine dyeshaving specific chemical structures. Further, the use of conventionalsuper sensitizers gives undesirable additive photosensitive spectrumranges to the color sensitizing sensitivity range of a silver halidephotographic emulsion containing a polymethine dye or the use of aconventional super sensitizer together with a polymethine dye increasesthe formation of fogs of a silver halide photographic emulsion. Theseproperties of such conventional super sensitizers are very inconvenientfor the production of photographic materials.

Therefore, an object of this invention is to provide a silver halidephotographic emulsion optically sensitized with a polymethine dye and aspecific super sensitizer without being accompanied with theabove-mentioned faults.

Another object of this invention is to provide a high optical sensitizerthat can be used effectively with polymethine dyes to increase the colorsensitivity of a silver halide photographic emulsion without increasingthe formation of fogs.

In accordance with the present invention, a silver halide photographicemulsion is incorporated with a methine dye and a compound shown by thegen ifll formula OHBCOO'" (I) wherein R represents an alkyl group having8 to 18 carbon atoms; R represents and p and q each represents 0 or apositive integer but p-l-q is 1-18. (If p or q is 0, R or Rrespectively, each represents CH COOH.) To increase, the colorsensitivity of the silver halide photographic emulsion.

Compound (I) in this invention is very effective for increasing thecolor sensitivity of a silver halide photographic emulsion when usedwith a polymethine dye. Further, the use of compound (I) of thisinvention does not give a tendency to giving undesirable photosensitivespectrum range to the silver halide photographic emulsion and giveslittle tendency to increasing the formation of fog,

Typical examples of polymethine dyes which can be effectively used withcompound (I) of this invention for increasing the color sensitivity of asilver halide photographic emulsion are shown by the following generalFormulas II to V.

wherein R and R each represents an alkyl group (such as methyl, ethyl,propyl, and butyl groups) or a substituted alkyl group (such asB-hydroxyethyl, fl-acetoxyethyl, B-sulfoethyl, 'y-sulfopropyl,6-sulfobutyl, carboxyethyl, ,8- sulfoethyl oxyethyl, allyl,butylsulfate, and benzyl groups); L L and L each represents a methinegroup (such as =CH, =C(CH =C(OCOCH 2 5) 2 5) 2- e 5) =C(C H and =C(C HCOOH); n represents 1 or 2; 121 represents a positive integer of 1 to 3;Z represents an atomic group necessary for forming 5- or 6-memberedheterocyclic ring, for example,

thiazoles (such as, thiazole, 4-methyl thiazole,

S-methyl thiazole,

5-phenyl thiazole,

4,5-dimethyl thiazole,

and 4- 2-thieny1) -thiazle benzothiazoles (such as, benzothiazole,4-chloro benzothiazole,

S-chloro benzothiazole,

6-chloro benzothiazole,

7-chloro benzothiazole,

4-methyl benzothiazole,

S-methyl benzothiazole,

6-methoxy benzothiazole,

S-ethoxy benzothiazole,

6-ethoxy benzothiazole, 4,5,6,7-tetrahydroxy benzothiazole,5,6-dimethoxy benzothiazole, -hydroxy benzothiazole,

4-phenyl benzothiazole,

5-phenyl benzothiazole,

6-phenyl benzothiazole,

and 5,6-diphenyl benzothiazole), naphthothiazoles (such as,a-naphthothiazole, li-naphthothiazole,

and S-methoxy-fl-naphthothiazole), oxazoles (such as, 4-methyl oxazole,S-methyl oxazole,

and 4-pheny1 oxazole), benzoxazoles (such as, benzoxazole, S-chlorobenzoxazole,

6-chloro benzoxazole,

4 S-hydroxy benzoxazole, 6-hydroxy benzoxazole, S-methoxy benzoxazole,5-phenyl benzoxazole, 5,6-diphenyl benzoxazole, and S-bromobenzoxazole)selenazoles (such as, 4-methyl selenazole and 4-phenyl selenazole),benzoselenazoles (such as, benzoselenazole, S-ethyl benzoselenazole,S-chloro benzoselenazole and S-methoxy benzoselenazole),naphthoselenazoles (such as, a-naphthoselenazole andfl-naphthoselenazole), naphthoxazole (such as, u-naphthoxazole andfl-naphthoxazole), thiazolines (such as, thiazoline, 4-methy1thiazoline, 4-hydroXymethyl-4-methyl thiazoline,4-acetoxymethyl-4-methyl thiazoline, and 4-acetoXymethyl-4-methylthiazoline), oxazolines (such as, oxazoline and 4-acetoxymethyl-4-methyloxazoline), selenazolines, 2-quin0lines (such as, 2-quinoline,6-methyl-2-quinoline, 7-methyl-2-quinoline, 8-methyl-2-quinoline.6-chloro-2-quinoline, S-chloro-Z-quinoline, 5-ethoxy-2-quinoline,6-ethoxy-2-quinoline, and 6-hydroxy-2-quinoline), 4-qu1'nolines (suchas, 4-quinoline, 6-methoxy-4-quinoline, 7-methyl-4-quinoline, and8-methyl-4-quin01ine), 3,3-dialkyl indolenines (such as, 3,3-dimethylindolenine), and

benzimidazoles (such as, l-ethyl benzimidazole, l-phenyl benzimidazole,1-ethyl-S-chlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole,1-hydroxyethyl-5,6-dichlorobenzimidazole, and1-ethyl-5-cyanobenzimidazole);

Z represents an atomic group necessary for forming a 5- or 6-memberedheterocyclic ring, for example, thiazoles, benzothiazoles,naphthothiazoles, oxazoles, benzoxazoles, selenazoles, benzoselenazoles,naphthoselenazoles, naphthoxazoles, thiazolines, 2-quinolines, andbenzimidazoles; d represents a positive integer of 1 to 3; at least oneof P and Q represents an organic substitutent such as CN and COOR (Rrepresents an alkyl group) or P and Q may be closed to form aheterocyclic ring, such as,

pyrazoles (such as, l-phenyl-3-rnethyl-5-pyrazolone andl-phenyl-S-pyrazolone),

iso-oxazolines,

oxyindoles,

2,4,6-triketohexahydropyrimidines (such as, barbiturlc acid and1-ethy1-2-thiobarbituric acid),

2-thio-2,4-thiazolidinediones (such as, 3-ethyl0-danine X represents aBr, 1-, SCN 0r C10; anion;

4-thiazolidones (such as, Z-ethyI-mercapto-4-thiazolinone,

and 2-alkylphenylamino-4-thiazolinone),

2-imino-2,4-oxazolidinediones,

2,4-imidazolidinediones (such as, 2,4-imidazolidinedione and3-cthyl-2,4-imidazolinedione),

2-thio-2,4-imidazolidinediones (such as, 2-thio-3-ethyl2,4-imidazolidinedione and 1,3-diethyl-2-thio-2,4-imidazolidinedione),

and S-imidazolinones;

and Y and Y each represents an atomic group such as, S, O--, -Se, andN(R necessary for forming a S-membered heterocyclic ring, such as,4-oxazolidine, 5-oxazolidine, 4-thiazolidinone, S-thiazolidinone,4-imidazolidinone, and the like. 1

By incorporating the above-mentioned compound (I) of this inventiontogether with one or more polymethine dyes shown by the above generalFormulas II, III, IV and V in a silver halide photographic emulsion, thecolor sensitizing sensitivity of the emulsion can be effectivelyincreased. 1

The increase of the color sensitivity of a silver halide photographicemulsion with the compound (I) of this invention shall be clearlydistinguished from the sensitization with polyalkyleneoxide derivativesdisclosed by Japanese publication No. 6,475/56. The polyalkyleneoxidederivataives shown by the patent can serve for only increasing theintrinsic sensitivity of a silver halide photographic emulsion but theycannot increase particularly only the color' sensitivity. On the otherhand, compound of this invention can, when it is used with a polymethinedye, increase remarkably the 'color sensitivity of a silver halidephotographic emulsion without or with slightly giving influences on theintrinsic sensitivity of the silver halide emulsion containing apolymethine dye.

The increase of the color sensitivity of a silver halide emulsion withthe compound (I) of this invention is far superior to the increase ofsensitivity of a silver halide photographic emulsion with a cationicsurface active agent of a quaternary ammonium salt form disclosed byU.S. Patents 2,271,623 and 2,334,864. That is, the cationicsurfaceactive agent shown by the US. patents increases mainly theintrinsic sensitivity of a silver halide photographic emulsion. In asilver halide photographic emulsion in which a polymethine dye isincorporated, there is a tendency that the relative sensitivity in along wave length side is highly increased. However, the addition of-sucha cation surface active agent is accompanied with the marked formationof fogs and, in particular, reduces the stability of photographicsensitive materials for preservation. On the other hand, the use ofcompound (I) of this invention give no infiuencesjor slightly weakinfluences, if any, on the intrinsic sensitivity of a silver halideemulsion and increases ,iefiectively only the color] sensitivity of thesilver halide emulsion. Further, by the use of compound (I) of thisinvention, fog formation is, not almost increased and the stabilityofphotographic sensitive materialsmade by the silver halide photographicemulsion for preservation are not eifected. Inthese points, the compound(I) of this invention is far superior to the cationic surface activeagent disclosed by the US. patents. As the silver halide photographicemulsion of which the color sensitizing sensitivity can be increasedwith compound (I) of this invention may be applied to silver chloride,silver bromochloride, silver bromide, silver bromoiodide, or silveriodochloride formedin gelatin, a derivative of gelatin, polyvinylalcohol, a water-soluble cellulose derivative, agar agar, zein, orahydrophilic colloid of a hydrophillic synthetic or natural resin. I

Compound (I) of this invention may be used as a form of intermolecularsalt or may be used as an inorganic acid added salt as well as a doublesalt form. Compound (I) or a salt of the compound may be added in asilver halide photographic emulsion as an aqueous solution, an alcoholsolution, or a solution in other solvent. The addition may beeffectively done in any steps of the production of the silver halidephotographic emulsion. However, greater effects can be obtained byadding the compound (I) in the silver halide photographic emulsionbefore adding a polymethine dye in the emulsion or as a mixture with apolymethine dye. In particular, in case where a water-soluble coupler ora dispersion of oil-soluble coupler is incorporated in a silver halidephotographic mulsion in the production of color photographic materials,it is necessary to add the compound (I) in the emulsion before theaddition of the coupler. The addition of compound (I) from 0.05 g. to 20g. is especially effective to obtain increase in color sensitivity.

The silver halide photographic emulsion to be incorporated with compound(I) and polymethine dye of this invention may be chemically sensitizedwith one or more chemical sensitizers, such as, a sulfur-containingsensitizer, e.g., allyl thiourea and allyl isothiourea, a reducingsensitizer, e.-g., imino-aminomethane sulfinic acid, a noble metalsensitizer, e.g., a salt of gold, platinum, and pallasium or a complexsalt thereof, and a sensitizer of a polyalkylene derivative, e.g., acondensation product of cetyl alcohol and polyalkylene oxide and acondensation product of nonyl phenol and poyalkylene oxide.

In the case of manufacturing the silver halide photographic emulsion thecolor sensitivity of which is increased with compound (I) of thisinvention, there may be added an anti-fogging agent, a stabilizer, acolor-toning agent, a hardening agent, a wetting agent, a plasticizer, adeveloping promoter, an irradiation preventing dye, a surface activeagent for coating, a fluorescent agent, a ultraviolet ray absorbing dye,a filter dye, and a coupler.

The practical examples of compound (I) of this invention are as follows:

CHzCOO' (Io) CHzCHzOH 'ntnowfi omomon orncoon H25C12-1G-CHzCOOH CH2COO-ngoou-u-ongongon These compounds may be synthesized by the processdescribed in Kogyo Kagaku Zassi, vol. 60, pages 104- (1957).

EXAMPLE 1 before being added with the polymethine dye and after lettingalone for 30 minutes at 40 C. was applied on a film support followed bydrying. A set of thus prepared samples were subjected to sensitometricexposure through a blue filter transmitting light of about 430 Nm. andanother set of the samples were subjected to sensitometric exposurethrough a red filter transmitting light having a wave length longer than600 Nm. These samples were then developed in a usual black and whitedeveloping solution containing methol and hydroquinone. Thus obtainedphotographic materials were examined about fogs and reactivesensitivity, which are shown in the following table.

TABLE 1 Blue Red exposure exposure Polymethine dye and eompd. (1)relative relative (g-lml. of AgX) sens. sns. Fog

(1) Dye (a), 0.37 100 100 0.17 (2) Dye (a), 0.37+compd. (Ia), 5.50 110158 0.18 (3) Dye (a), 0.37+compd. (1b), 5 50 105 151 0.19 (4) Dye (a),0.37+compd. (1c), 5 50 98 123 0. 17 (5) Dye (a), 0.37+compd. (Id), 5 5100 123 0.17 (6) Dye (a), 0.37+compd. (1e), 5.50-- 93 162 0.17 (7) Dye(a), 0.37+compd. (If), 5.50 107 135 0. 17 (8) Dye (a), 0.37+crnpd. (Ib),5.50 100 125 0.17

where dye (a) was CH2CI'I2OCOCII3 CHzCHzOCOCH EXAMPLE 2 A silveriodobromide gelatin emulsion as in Example 1 was added with a methanolsolution of compound (I) and a polymethine dye shown by Formula 11, letalone for 60 minutes at 40 C., and after being added with a stabilizer,a hardening agent, and 20 parts of a aqueous solution of1-hydroxy-4-sulfo-4-N-octadecyl-2-naphthoamide, applied on a filmsupport followed by drying. The film was then subjected to sensitometricexposure as in Example 1, color-developed using N,N-diethylaminoaniline, and subjected to usual bleaching and fixing treatments toform a cyan color image. Thus obtained films were examined about fogsand relative sensitivities,

the results of which are shown in the following table.

TABLE 2 Blue Red exposure exposure Polymethine dye and compd. (1)relative relative (g./mo1 AgX) sens. sens. Fog

(1) Dye (b), 0.50 100 100 0. 21 (2) Dye (b), 0.50+cornpd. (If), 1.40-...98 123 0. 22 (3) Dye (b), 0.50+oompd. (II), 5.50 93 135 0.22

(4) Dye (c), 0.50 100 100 0. 17 (5) Dye (0), 050+ cornpd. (Id), 2.50 98151 0. 17

(6) Dye (d), 0.30; dye (e), 0.10 100 100 0. 18 (7) Dye (d), 0.30; dye(e), 0.10-j-(Id), 2.50 100 174 0.18

where dye (b) was C=CHG==CHC 01 CHzCH-CHzO CH3 CHaCHCHzO CH3 0 0 11 80 0O HeSOaNa 8 dye (c) was s C H /s 2 5 C=CH( 3=OHO Br i 1 CH3 CH3 dye (d)was 2 5 L C=CH( I=OHC Bri U C2115 CgHs and dye (e) was S S CzHs\O=OH(|J=CHC/ Brorno OCH3 N f (E2H4OH CzHqOH EXAMPLE 3 Silverbromochloride gelatin emulsion which had been prepared in accordancewith a conventional method were added with the polymethine dyes shown byFormulas II, III, IV and V and, after letting alone for 30 minutes at 35C., applied on film supports followed by drying.

While, same emulsions were added with compound (I) together with thepolymethine dyes of the Formulas II, III, IV and V and after lettingalone under the same conditions, applied on film supports followed bydrying. Thus prepared samples were subjected to sensitometric exposurethrough a yellow filter absorbing light of wave length shorter than 500Nm., and then treated with a black and white developing solutioncontaining methol and hydroquinone. Thus obtained films were examinedabout fogs and relative sensitivities, the results of which are shownbelow.

TABLE 3 Yellow exposure sensi- Polymethine dye and compd. (I) (g./molAgX) tivity Fog (1) Dye (f), 0.30 0. 09 (2) Dye (f), 0.30+cornpd. (If),3.50 155 0. 10

(3) Dye (g), 0.30 100 0. 08 (4) Dye (g), 0.30+compd. (If), 3.50 141 0.13

(5) Dye (h), 0.30 100 0. 08 (6) Dye (h), 0.30+compd. (10,350.- 0.14

(7) Dye (e), 0.30 100 0. 16 (8) Dye (e), 0.30+compd. (11), 3.50 0.18

(9) Dye (i), 0.30 100 0. 08 (10) Dye (i), 0.30+compd. (If), 3.50.- 1380. 12

(11) Dye (j), 0.30-l-compd. (II), 3.50.. 100 0.10 (12) Dye (j),0.30+compd. (If), 3.50 132 0. 12

(13) Dye (k), 0.30+compd. (If), 3.50 100 0.13 (14) Dye (k), 0.30+eornpd.(If), 3.50 141 0.20

15) Dye 1 0.30 100 0.08 (16) Dye (l), 0.30+compd. (If), 3.50-. 126 0. 09

(17) Dye (m), 0.30 100 0. 09 (18) Dye (m), 0.30+cornpd. (II), 3.50 1410. 12

where dye (f) was OH? I- r r 01H 02H! dye (g) was own-011:0. x

dye (j) was CzHs (k) was Hat-cam. I

dye (l) was CH3 I EXAMPLE 4 The silver bromochloride gelatin emulsion asin Example 3 was added with 0.25 g./mol AgX of 9-ethyl-5,5'-diphenyl-3,3'-bis-sulfobutyl oxacarboxycyanine pyridinium salt, letalone for 30 minutes at 35 C., and added with a stabilizer and ahardening agent. The emulsion was then further added with 30 g./mol AgXof 1-(4-phenoxy- 3-sulfophenyl)-3-heptadecyl-5-pyrazone and applied on afilm support followed by drying.

In this case, before adding the polymethine dye, a set of the emulsionwas added with 1-2 g./mol AgX of compound (If) and another set of theemulsion was added with 1-2 g./mol AgX of dodecyl-trimethyl ammoniumbromide.

A set of these samples were subjected to sensitometry exposure through ablue filter transmitting light of about 430 Nm. and another set of thesamples were subjected to sensitometry exposure through a green filtertransmitting light of about 550 Nm. and then they were colordevelopedusing N,N-diethylamino aniline to form a magenta color image. Thesamples were then examined about fogs and relative sensitivities. Theresults are shown in the following table.

TABLE 4 Blue Green exposure exposure relative relative sensisensi-Additive (g./mol AgX) tivity tivity Fog None 100 0. 09 Cornpd. (II),1.0... 102 138 0.09 Compd. (If), 2.0... 114 0.09 Dodecyltrimethylammonium bromide, 10 129 138 0.12 Dodeoyltrimethyl ammonium bromide,2.0. 140 140 0. 24

EXAMPLE 5 A mixture of g. of a 0.06% methanol solution of thepolymethine dye (11) shown below and 2.5 to 80 g. of a 2% methanolsolution of compound (If) was added in 1 kg. of an emulsion containing0.85 mol of silver iodobromide and chemically sensitized with asulfur-containing sensitizer and a gold salt-containing sensitizer by aconventional method and, after letting alone for 30 minutes at 40 C.,the emulsion was added with a usual stabilizer, a hardening agent, andthen 200 parts of an aqueous 5% solution of1-hydroxy-4-sulfo-N-octadecyl- 2-naphthamide as a coupler.

The prepared coating solution was coated upon a film support and dried.The coated sample Was exposed and developed as in Example 2. The resultsfor detecting the fog and the relative sensitivity are shown in Table 5.

' olmsoiuficam EXAMPLE 6 Into 1 kg. of an emulsion containing 0.15 molof silver chlorobromide prepared by a conventional method was added amixture of 30 g. of a methanol solution of 0.1% of9-ethyl-5,5'-diphenyl-3,3'-bis-sulfobutyl oxacarbocyanine-pyridiniumsalt and 15 to 150 g. of a 2% methanol solution of compound (Ib) andthen the emulsion was added with 7 g. ofl-(4-phenoxy-3-sulfophenyl)-3-heptadecyl-5-pyrazolone as a coupler. Theemulsion was, after letting alone for 30 minutes at 35 C., coated upon afilm support and dried. The values of fog and relative sensitivityobtained by testing as in Example 4 are shown in Table 6.

What is claimed is:

1. A gelatino-silver halide photographic emulsion containing a methinedye and a compound having the general Formula I:

R1 n-f r rq omooowherein in Formula I R represents an alkyl group having8 to 18 carbon atoms; R represents(CH CH O) H; R represents (CH CH O) H,p and q each represents a cardinal number including 0, and p-l-q equals1 to 18, provided that when p is zero R is CH COOH and when q is zero Ris -CH COOH, said methine dye having a general formula selected from thegroup consisting of:

wherein in Formulas II and III L L and L each represents a methinegroup, n is an integer of from 1 to 2, m is an integer of from 1 to 3, Xis an anion selected from the group consisting of Br', 1*, SCN- and C10Z and Z are each selected from the class consisting of atomic groupsnecessary for forming heterocyclic rings having 5 to 6 members, a is aninteger of from 1 to 3, P and Q taken together are the atomic groupsnecessary for forming heterocyclic rings having 5 members and containingin the ring 3 carbon atoms, one nitrogen atom and one of nitrogen,sulfur and oxygen atoms and R and R are each selected from the classconsisting of alkyl groups, allyl groups and substituted alkyl groups,said substituents being selected from the class consisting of hydroxy,acetoxy, sulfo, carboxy, alkoxy, sulfate and phenyl groups.

2. The emulsion as claimed in claim 1 wherein said emulsion contains thecompound shown by the general Formula I in an amount of about 0.05 g. to20 g. per 1 mol of silver halide.

3. The emulsion as claimed in claim 1, wherein said methine dye has theformula wherein R and R are each selected from the class consisting ofalkyl groups, allyl groups, and substituted alkyl groups; saidsubstituents being selected from the class consisting of hydroxy,acetoxy, sulfo, carboxy, alkoxy, sulfate and phenyl groups; L L and Leach represents a methine group; ,X is an anion selected from the class12 consisting of BF, 1*, SCN- and C10 Z and Z are each selected from theclass consisting of atomic groups necesary for forming heterocyclicrings having 5 to 6 members; It is an integer from 1 to 2; and m is aninteger from 1 to 3, v

4. The emulsion as claimed in claim 1, wherein said methine dye has theformula rzi 1 P R1 1'-I oH=oH n-1-o:(L, L,)d 1=o 'Q wherein R isselected from the group consisting of alkyl groups, allkyl groupsandsubstituted alkyl groups," said substituents being selected from theclassconsisting of hydroxy, acetoxy, sulfo, carboxy, alkoxy', sulfateand phenyl groups; L and L each represents a methine group; Z isselected from the class consisting of atomic groups necessary forforming 'heterocyclic rings-having from 5 to 6 members; P and Q takentogether are the atomic groups necessary for forming heterocyclicringshaving 5 members and containing in the ring 3carbon atoms, one nitrogenatom and one of nitrogen, sulfur and oxygen atoms; 21 is in integer from1 to 2, and d is an integer from 1 to 3.

5. The emulsion as claimed in claim 1, wherein said compound shown bythe Formula I is:

(CHzCHzQ) H H C l I(CHzOH;O) H

CHnCOO' wherein p+q is 18.

6. The emulsion as claimed in claim 1, wherein said compound shown bythe Formula I is:

(CHzCHzOhH H,,o,2 fi oHzoH,o),H

wherein p-l-q is 10.

- 7. The emulsion as claimed in claim 1, wherein said compound shown bythe Formula I is:

zC zOhH Hi5c,ifi cH1cHio)qH 0111000- wherein p+q is 5.

References Cited UNITED STATES PATENTS 2,271,623 2/1942 Carroll 961043,113,026 12/1963 Sprung 96107 I. TRAVIS BROWN, Primary Examiner Us.'01; X.R.

